MS CHAUHAN ADVANCE

300 (e) CH3SO3– ANSWERS — LEVEL 2 1. d 2. c The reaction is Finkelstein reaction. 3. (a) F– ; (b) I– ; (c) F– ; (d) NH2—NH2 ; Br Ph 4. (a) CH 3 - Br | (c) H Br H CH3 (b) CH 3 - CH - CH 3 Ph Ph Br H Br CH | (d) Br CH3 (e) C–CH2–CH3 Ph Br 5. (a) CH2–Br (b) Br (c) Cl Cl (d) (e) 6. a – p, w; b – q, x ; c – r, y; d – s, z 7. a – r, s; b – p, q; c – r, s; d – r, s 8. (a) (b) (CH 3)3C - I Br Br (c) 9. (1) Br (2) I (3) Cl 10. (X) A- reactants, B-transition state, C-Inter mediate, D- transition state (Y) (i) exothermic (ii) B (iii) F (iv) a https://t.me/studyzee

301 11. A – b; B – b; C – d; D – a; E – b; F – b; G – b 12. A – c, d, e, f, h; B – b, c, f, i ; C – a, g, j 13. Part – 1234 5 I Reaction– A DE G h, 14. Yes – a, b, c, d, f, No – e, g, i, j, k 15. a–p, q, r, s, t; b–p,s,t; c–p, q, r t; d–p 16. 2 17. a – p, r; b – q; c – s; d – r 18. a – q; b – p; c – r; d – q 19. a – p; b – r; c – s; d – s 20. A – c; B – a https://t.me/studyzee

302 5B ALKYL HALIDES Elimination Reactions (E1,E2,E1CB ,Ei ) Level - 1 1. Which of the following alkyl halide gives only one product (excluding stereoisomer) when undergo E 2 reaction ? (E 2 = elimination bi-molecular) Cl Cl (a) (b) (c) (d) 2. Cl E2 reaction X Cl + (Hoffmann product) (Saytzeff product) (A)In the above reaction, maximum Saytzeff product will obtained when : (a) X = -I (b) X = -Cl (c) X = -Br (d) X = -F (B) In the above reaction Hoffmann product is major when X is : (a) -I (b) – Cl (c) – Br (d) – F https://t.me/studyzee

303 3. O N H(P) | when (P) undergoes Hoffmann exhaustive methylation (twice) then the product obtained will be : H | ON (a) (b) (c) (d) O- O NMe2 NMe2 + 4. ¾¾he¾at ®( A), ¾¾he¾at ® (B) , Ph Ei 98% Ph Ei 85% (syn) (Anti) Ph Ph (P) (Q) Product (A) & (B) of the above reaction is : (a) A = P, B = P (b) A = Q, B = Q (c) A = P, B = Q (d) A = Q, B = P CH3 5. HO– Major product of the reaction is : D OTs (a) (b) (c) (d) 6. Which of these dehydrates most easily ? (b) CH3 (a) CH 3 — CH 2 — CH 2 — OH OH CH3 | (c) OH (d) CH 3 —C — CH 2 — OH 7. | CH3 CH3 ¾¾N¾aOC¾H3¾¾® Product; Product of the reaction is : CH 3OH Br (E2 reaction) CH3 (a) (b) (c) (d) No reaction OCH3 https://t.me/studyzee

304 A NMe3 (Major) HO- 8. D Major product A is : (a) (b) (c) (d) (c) (d) OH 9. H2SO4 A D (Major) Major product A is : (a) (b) 10. In which of the following reaction Saytzeff alkene is major product ? CH3 | (a) CH 3 - CH 2 -C Å ¾¾HO¾- ® (b) CH 3 - CH 2 - CH 2 - CH - CH 3 ¾¾EtO¾- ® | | -NMe 3 D D CH3 F C|H3 Br | ¾t¾-BuD¾O¾K ® ¾C¾H3¾O¾K ® (c) CH 3 - CH 2 -C - CH 3 (d) CH 3 - CH 2 - CH 2 - C - CH 3 | | D Br CH3 CH3 Ph H alc. KOH 11. Br (E2 reaction) Major product of the reaction is : Ph CH3 CH3 Ph Ph Ph CH3 CH3 (a) C = C (b) C = C Ph CH3 CH3 Ph Ph – CH - CH - Ph CH3 (d) | | (c) C = C Ph CH 3 OH 12. The conversion of 2, 3-dibromobutane to 2-butene with Zn is : (a) Redox reaction (b) a-Elimination (c) b-Elimination (d) Both a-elimination and redox reaction https://t.me/studyzee

305 13. 1, 3-Dibromopropane is heated with zinc dust in ether. The product formed is : (a) propene (b) propane (c) cyclopropane (d) 3-bromopropane O Br 14. Reaction (1) ¾¾alc.¾KO¾H ® (A) (major) O Reaction (2) ¾¾alc.¾KO¾H ® (B) (major) Br O Reaction (3) ¾¾alc.¾KO¾H ® (C) (major) Br Product obtained in above reactions (1), (2) & (3) is : (a) A = B but C is different (b) A = C, but B is different (c) B = C, but A is different (d) A = B = C all product are identical Cl Cl Cl 15. Reaction (1) Cl Cl ¾¾3 m¾ole¾alc¾. KO¾¾H ® (A) Cl Cl Cl Cl Reaction (2) Cl Cl ¾¾3 m¾ole¾alc¾. KO¾¾H ® (B) Cl Cl Cl Cl Reaction (3) Cl Cl ¾¾3 m¾ole¾alc¾. KO¾¾H ® (C) Cl Product obtained in above reactions (1), (2) & (3) is : (a) A = B, C is different (b) A = C, B is different (c) B = C, A is different (d) A = B = C is same https://t.me/studyzee

306 ¾al¾c. K¾OH® ( x) 16. x is number of E2 product obtained Br (including stereoisomers) Find (x). (a) 3 (b) 4 (c) 5 (d) 6 (c) (d) CH 3 | ¾¾EtDO¾H ® ( A) 17. CH 3 ¾ C¾ CH ¾ CH 3 | | CH 3 Br Major product (A) is : (a) (b) 18. Which one of the following compound will be least susceptible to elimination of hydrogen bromide ? (a) Br — CH 2 — CH 2 — NO 2 (b) Br — CH 2 — CH 2 — CH 3 (c) Br — CH 2 — CH 2 — CN (d) Br — CH 2 — CH 2 — CO 2Et 19. Two alkenes, X(91% yield) and Y(9% yield) are formed when the following compound is heated. CH3 ¾¾D ® X + Y 91% 9% N(CH3)3OH The structures of X and Y, respectively are : (a) CH3 and CH2 (b) CH3 and CH3 (c) CH2 and CH3 (d) CH3 and CH2 20. In the dehydrohalogenation of 2-bromobutane; which conformation leads to the formation of cis-2-butene ? CH3 CH3 CH3 CH3 H CH3 H CH3 HH CH3 H (a) (b) (c) (d) H Br Br H Br H H Br H H CH3 H O–H O 21. CH3 – C – Cl (2 mole) (A) (Ei) (B) + CH3CO2H D Pyridine O–H https://t.me/studyzee

307 Product (B) of given reaction is: (a) (b) (c) (d) 22. What product will be formed from Hoffmann exhaustive methylation of following compound? Me 2CHCH 2NHCH 2CH 2Me (i) CH3 -I (excess) Product ¾¾¾¾¾¾® (ii) Ag 2O (iii) D (a) Me — CH == CH 2 (b) H 2C == CH 2 (c) CH 3 — C == CH 2 (d) CH 3 — CH — CH == CH 2 | | CH 3 Me CH2 OH 23. ¾H¾Dr® ( A) Product (A) is : (a) (b) (c) (d) CH3 24. Hr ; Products obtained are : ¾¾D ® OH (a) Racemic (b) Diastereomers (c) G.I (d) Positional isomers CH3 25. ¾¾N¾aO¾Et¾® ; Major product of the reaction is : (E 2reaction) Cl CH3 CH3 CH3 CH3 (a) (b) (c) (d) https://t.me/studyzee

308 CH3 26. Cl ¾N¾aO¾Et® ; Major product of the reaction is : CH3 CH3 CH3 CH3 (d) (a) (b) (c) 27. The E 2 product of the following reaction will be ? H CH3 NaOH H Br H CH3 OH CH3 (a) (b) OH H HH (c) CH3 (d) CH3 H 28. An halide C 5H11Br on treatment with alc. KOH give 2-pentene only. The halide will be : (a) CH 3 - CH 2 - CH 2 - CH 2 - CH 2 - Br (b) CH 3 - CH 2 - CH 2 - CH- CH 3 | CH 3 Br | (c) CH 3 - CH 2 - CH- CH 2 - CH 3 (d) CH 3 - CH - C - CH 3 | | Br Br 29. End product (D) in the given sequence is: ¾C¾H ¾3 NH¾CH¾3 ®( CH 3 I ¾Ag¾2O ¾H2®O (D) ¾(2m¾ol¾ar ¾equ¾iva¾len®t) (C) Br Br 2 molar equivalent A) ¾B¾aO®( B) + (CH 3 ) 3 N (a) O CH3 (b) (c) (d) O OH https://t.me/studyzee

309 30. For each of the following pairs of E 2 reaction, select the one that occurs with the greater rate constant. CH 3 CH 3 | | (1) CH 3CH 2CH 2Cl + CH 3 - C - O - (2) CH 3CH 2CH 2I + CH 3 - C - O - | | CH 3 CH 3 (3) H 3C - CH - CH 3 + CH 3O - (4) H 3C - CH- CH 3 + CH 3S- | | Br Br Br (5) Br + –OH` (6) + –OH (a) 2, 4, 6 (b) 1, 3, 5 (c) 2, 3, 5 (d) 2, 4, 5 Br Br 31. | | ¾ CH 3 ¾xN¾aN¾H®2 ¾y¾CH¾3I® CH 3 ¾ C ºº C ¾ C ºº C ¾ CH 3 CH 3 ¾ C ¾C || Br Br x and y mole consumed. Value of x + y = (b) 6 (c) 7 (d) 8 (a) 5 32. The following bimolecular elimination reaction (E 2) is carried out with different halogen leaving groups. The per cent yield of the two products (2-hexene and 1-hexene) for each leaving group is listed below. X + CH3O– E2 + Leaving group Conj. Acid pK a %-yield of 2-hexene %-yield of 1-hexene X =I – 10 81% 19% X = Br – 9 72% 28% X = Cl – 7 67% 33% X =F 3.2 30% 70% Which of the following statement is (are) true concerning this series of E 2 reactions ? (a) Based on the pK a 's of the conjugate acid, I- is the best leaving group and F - is the poorest leaving group (b) When I- , Br - and Cl - are used as leaving groups, Zaitsev's rule is followed (c) F - is the strongest base (and therefore the poorest leaving group) and the transition state for reaction with fluoride as the leaving group has the least double bond character https://t.me/studyzee

310 (1) CH3 – I A (d) a, b, c are true (2) Ag2O B (3) D N(CN3)2 33. ((21))DH2 O2 H D Product ( A) & (B) respectively are : H H H H (a) & D (b) & H H H D D H H H (c) & H (d) & H D (1) MeI (2) AgOH 34. N Me OH ¾co¾nc.¾H2¾SO®4 ( A) (B) (1) MeI (C) ¾¾¾¾® (3) D ¾¾¾¾® (2) AgOH (3) D Product in above reaction is : Me – N – Me (a) (b) (c) (d) 35. Major product obtained in the reaction of 1-phenyl-2-bromobutane with NaOMe is : (a) (E)-1-phenylbut-1-ene (b) (E)-1-phenylbut-2-ene (c) 1-phenyl-2-ethoxybutane (d) (Z)-1-phenylbut-2-ene 36. Which of the following alkyl halides give most complex mixture of alkene in an E 2 reaction ? (a) CH 3 - CH 2 - CH 2 - CH 2 - Br (b) CH 3 - CH 2 - CH 2 - CH - CH 3 | Br CH 3 | (c) CH 3 - CH 2 - CH - CH 2 - CH 3 (d) CH 3 - C - CH 2 - CH 3 | | Br Br H Br CH3 D 37. H H ¾¾alc.¾KO¾H ® ( A) (major) Product (A) is : https://t.me/studyzee

OH 311 D CH3 D D (d) (a) H (b) (c) OH Hr OH ¾¾D ® 38. ( A) ; Hr ( B) ¾¾D ® Sum of number of a-hydrogen present is compound A + B is : (a) 18 (b) 19 (c) 20 (d) 21 39. ( A) ¾(¾1) ¾exc¾ess¾CH¾3I¾K 2¾CO¾3 ®(B) (i) excessCH3I K 2CO3 H 2C = CH -CH - CH = CH 2 | (2) Ag 2O H2O ¾(¾ii) ¾Ag¾2O ¾¾¾¾® (iii) D (3) D CH3 Identify A : (a) (b) (c) N (d) | NN H N || | HH H Br | 40. CH 3 — CH 2 — C — CH 2 — Et ¾¾alc.¾KO¾H ® ( A) | (major) CH 2(n - Pr) n - Pr = n - propyl Product (A) is : Me Et Me Et Me Et Me Et (d) (a) (b) (c) Pr H H Pr Pr Pr Ph OH 41. ¾¾H3DP¾O¾4 ® Major product obtained by dehydration of given alcohol is : https://t.me/studyzee

312 Ph Ph Ph Ph (b) (c) (d) (a) Br 42. O ¾¾NaO¾CH¾3 (¾2 m¾ol¾e) ®( A) ¾¾H3O¾¾Å ®(B) Br CH 3OH Product (B) of above reaction is : OH OH OH OH (a) (b) (c) (d) OH OH OCH3 43. Ph — CH— CH 2 — CH 2 ¾Z¾n-¾C¾u ® Product | | D Br Br Product of the above reaction is : (b) Ph (d) Ph — C ºº C — CH 3 (a) Ph — CH == CH — CH 2 — Br (c) PH — CHBr — CH == CH 2 OH Hr ¾¾D ® 44. ( A) OH Product (A) is : (a) (b) (c) (d) H Ph H 45. Ph ¾¾NaDO¾¾Et ® Me NMe3 Major product of the above reaction is : https://t.me/studyzee

313 Ph C == C Ph Ph C == C Ph (a) Ph (b) Me Ph Ph Ph H Me Me (c) C == C Ph (d) C == C Me Ph OEt LDA 46. A + N2 + Ph – CH = CH2, Product A is: N NH — CH2 — CH2 — Ph LDA = Lithium di-isopropyl amide (a) (b) (c) (d) N | 47. H Major product of the reaction, when the given compound undergoes Hoffmann exhaustive methylation is : (a) (b) (c) (d) H 2C == CH 2 CH3 H H OH ¾¾PPyOri¾Cdiln¾3e ® Major product of the reaction is : 48. H H (a) CH3 CH3 (b) H https://t.me/studyzee

314 CH3 H H (c) Ph Ph (d) H C = CH – C – OH H Cl 49. ¾¾H¾+ ® Product D Stereochemistry of the product is : (b) Racemic mixture (d) Optically pure enantiomers (a) Meso compound (c) Diastereomer CH3 50. O O Which of the following reactant is used to obtain above compound (A). (Assume that EtO - is used in all the reaction) H Br H CH3 CH3 Br CH3 Br CH3 Br H H (a) O (b) O (c) O (d) O O OOO HH 51. Cl OH ¾¾alc.¾KO¾¾H ®( A), Product A is : HH O OH (a) (b) O (c) (d) Cl 52. Rank the following in order of decreasing rate in an E 2 reaction: CH3 CH3 CH3 Br Br Br (d) b > a > c CH3 (c) (a) (b) (a) a > b >c (b) c > a > b (c) c > b > a https://t.me/studyzee

315 53. Ph ¾ ¾EtKOO¾HH,¾D ® ( A) , Product (A) is : F (major) (a) Ph (b) Ph (c) Ph (d) Ph OEt OH 54. ¾Et¾ODs® ( A) Major (b) Positional isomer Br (d) Chain isomer Nr Me3 ¾Et¾ODs® (B) Major Relation between (A) and (B) is : (a) G.I. (c) Enantiomer 55. Cl ¾¾3Na¾NH¾2 ® Product ; The Product is : O liq. NH3 (a) CH2 (b) HC ºº C — (CH 2 )3 ONa O (c) NaC ºº C — (CH 2 )3 ONa (d) H — C ºº C — (CH 2 )3 OH 56. Which best describes the product of the following reaction ? CH3 Ph CD3 ¾ ¾K+t¾-B¾uO¾- ® product Br E2 (a) Absolute configuration has been inverted (b) Absolute configuration has been retained (c) Racemization (loss of absolute configuration) has occurred (d) Loss of chirality has occurred (the product is achiral) 57. What is the major product of the following reaction ? OH CH3 | CH3 – CH2 – C – CH ¾¾H¾+ ® Product | CH3 CH3 D https://t.me/studyzee

316 H CH3 | CH3 (b) C = C CH – CH3 | CH3 CH3 CH – CH3 CH3 (a) C = C H CH3 H CH3 CH3 CH3 | (c) C=C CH – CH3 (d) C = C H CH3CH2 CH3 CH2CH3 58. What will be the major product of each of the two reaction shown below ? 1. CH3CH2CHCH3 heat +N(CH3)3–OH CH3CH=CHCH3+CH3CH2CH=CH2 2. CH3CH2CHCH3+ CH3CH2ONa heat XY Br (b) 1 – Y, 2 – X (c) 1 – X, 2 – Y (d) 1 – Y, 2 – Y (a) 1 – X, 2 – X NHCH2CH3 59. + CH3I (excess) ¾® product; The product is : (a) a primary amine (b) a tertiary amine (c) a secondary amine (d) a quaternary ammonium salt CH2–OH OH 60. ¾¾H¾+ ®( A) ¾¾Isom¾er¾isat¾io¾n ®(B) D (A) on heating isomerizes to (B). What is the structure of (B) ? CH3 (a) (b) (c) (d) H | Ph—C—Ph 61. CH2–CH2–OH ¾¾H¾+ ® ( A) , major product (A) is : D (major) https://t.me/studyzee

317 Ph—C—Ph Ph—CH—Ph CH2–CH3 CH–CH3 (a) (b) Ph—CH—Ph Ph CH–CH2 Ph—CH—OH (c) CH2–CH3 (d) 62. Which of the following carbocation will undergo rearrangement ? CH3 Å (a) (b) Å CH3 – Å = Å – (c) CH – C O (d) CH3 – NH – CH CH – CH3 | | CH3 CH3 63. In which of the following reaction resonance stabilized product will form ? CH2–OH OH (a) ¾¾H¾+ ® (b) ¾¾H¾+ ® D D CH3 (c) OH ¾¾H¾D+ ® (d) All of these 64. In which of following reaction rearrangement take place with change in carbon skeleton ? (a) CH3 — C|H3 Å (b) CH 3 - CH 2CH 2Å C — CH2 | CH3 CH3 CH2 Å (d) CH 3 - CH Å - CH 3 – CH – – CH2 (c) | CH3 https://t.me/studyzee

318 65. Consider the following reaction : H3PO4 OH heat Which response contains all the correct statement about this process ? (1) Dehydration (2) E 2 mechanism (3) Carbon skeleton migration (4) Most stable alkene will form (5) Single-step reaction (a) 1, 3 (b) 1, 2, 3 (c) 1, 2, 5 (d) 1, 3, 4 CH3 H Br ¾¾HB¾r ® ( X ) ¾¾acNe¾taoIn¾e ® (Y) (Major); Product (Y) is: 66. H OH CH3 (b) trans-2-butene (a) cis-2-butene (c) 1-butene (d) Iso-butene Br Br || 67. CH 2 — CH == CH — CH 2 ¾Z¾n ¾(du¾s¾t) ®( A) Above reaction is an example of 1,4-elimination. Predict the product. (a) CH 3 — CH == C == CH 2 (b) CH 3 — C ºº C — CH 3 (c) CH 3 — CH 2 — C ºº CH (d) H 2C == CH — CH == CH 2 Ph 68. ¾¾con¾c. H¾2S¾O¾4 ® Major product of the reaction is: Ph OH Ph (a) Ph (b) Ph Ph Ph (c) (d) None of these Ph https://t.me/studyzee

319 Ph CH 3 Ph Et || || 69. Ph — C — C — CH 3 + Ph — C — C — Et ¾¾H2S¾O¾4 ® || || OH OH OH OH (A) (B) Ph O Ph O | || (p) Ph — C — C — CH 3 | || | (q) Ph — C — C — Et CH 3 | Et Ph O Ph O | || (r) Ph — C — C — CH 3 | || | (s) Ph — C — C — Et Et | CH 3 When (A) and (B) reacts with H 2SO 4 products obtained are : (a) p, q, r, s (b) p, q (c) p, q, r (d) p, q, s 70. Which of the following compound gives even number of Hoffmann’s exhaustive methylation and elimination? (a) (b) (c) (d) NH N N N | | H H CH3 I alc.KOH X = Number of chiral products (including stereoisomer). C C CH2 71. CH3 CH—CH3 (a) 2 CH3 (c) 6 (d) 8 Cl (b) 4 72. t-butOs (A) ; “( A)” is : O t-butO https://t.me/studyzee

320 Os t-but O (b) (a) O Cl O t-but (c) (d) OO 73. ¾C¾on¾c. H¾2S¾O¾4 ® A + H 2O (Major) OH which of the following is product “A” in the above reaction? (a) (b) (c) (d) 74. Which of the following is true regarding increasing reactivity in the E 2 reaction with Na + C2H5O- ? CH3 CD3 CH3 CH3 — C — Br D3C — C — Cl H3C — C — Cl CH3 CD3 CH3 (A) (B) (C) (a) A is more reactive than B (b) B is more reactive than A (c) A is more reactive than C (d) B is less reactive than C 75. EtO r1 Br EtO C =CH2 r2 | D Br DD https://t.me/studyzee

321 Compare rate of Reactions. (a) r1 > r2 (b) r1 = r2 (c) r2 > r1 (d) r1 = r2 76. Ph OH HÅ Ph + Ph 2 | Which statement is not true for above reaction ? (a) It is dehydration reaction. (b) The mechanism followed by reaction is E1 (c) The reaction is stereo selective. (d) The major product is Z-alkene. ANSWERS — LEVEL 1 1. (d) 2. A -a 3. (a ) 4. (c) 5. (b) 6. (b) 7. (d) 8. (b) 9. (c) B- d 11. (c) 12. (c) 13. (c) 14. (d) 15. (d) 16. (c) 17. (b) 22. (a) 23. (b) 24. (a) 25. (b) 10. (d) 30. (c) 31. (d) 32. (d) 33. (a) 38. (c) 39. (c) 40. (c) 41. (c) 18. (b) 19. (c) 20. (a) 21. (b) 46. (a) 47. (d) 48. (b) 49. (b) 54. (b) 55. (c) 56. (d) 57. (d) 26. (a) 27. (d) 28. (c) 29. (b) 62. (b) 63. (d) 64. (a) 65. (d) 70. (a,b) 71. (b) 72. (b) 73. (a) 34. (a) 35. (a) 36. (b) 37. (c) 42. (b) 43. (b) 44. (b) 45. (c) 50. (a) 51. (c) 52. (b) 53. (b) 58. (b) 59. (d) 60. (b) 61. (a) 66. (b) 67. (d) 68. (b) 69. (b) 74. (a,c,d) 75. (a) 76. (d) https://t.me/studyzee

322 Level - 2 1. Comprehension E 2 reaction ® Elimination bimolecular In the general mechanism of the E 2 reaction a strong base abstract a proton on a carbon atom adjacent to the one of the leaving group. As the base abstracts a proton, a double bond forms and the leaving group leaves. CH3 ¾C¾H3¾ON¾a ® H + H CH 3 - CH 2 - CH - CH 3 CH3OH + | CH3 Br (major) Mechanism : Q H dQ + | + CH3ONa + CH3O----H CH3 – CH – CH – CH3 CH3–— CH CH — CH | BrdQ Br anti-coplanar transition state (staggered conformation -lower energy) (trans-2-butene) A. Identify the rate of reaction of given compounds in E 2 reaction: I Br Cl F (a) (b) (c) (d) (a) a > b > c > d (b) a > c > b > d (c) b > a > c > d (d) b > d > a > c B. In given pairs, which compound is more reactive toward E2 reaction: CH3 CH3 Br Br (P) (I) CH3 (II) (Q) CH3 – CH – CH3 CH3 – CH – CD3 | | Br Br (III) (IV) https://t.me/studyzee

Br 323 (R) Br (V) (VI) (S) Ph —CH2—CH2 —Br Ph — CH — CH3 | (VII ) Br (VIII) (a) P – II, Q – III, R – VI , S – VII (b) P – II , Q – III, R – VI , S – VI (c) P – I, Q – III , R – VI , S – VII (d) P – I , Q – II , R – V , S – VIII Ph H ¾¾alc.¾KO¾H ® ( A) , Ph H ¾¾alc.¾KO¾H ® (B) C. CH3 Br CH3 CH3 Br CH3 Ph Ph Product (A) and (B) are : (b) A = trans, B = cis (a) A = cis, B = cis (d) A = cis, B = trans (c) A = trans, B = trans CH3 CH3 D. ¾¾NaO¾¾Et ®( A) , ¾¾NaO¾¾Et ®(B) D D Cl Cl Select the products (A) and (B) from the compounds (P) and (Q) given below: CH3 CH3 (P) (Q) (a) A = P, B = P (b) A = Q, B = Q (c) A = Q, B = P (d) A = P, B = Q E. Which of the following compound is inert toward E2 reaction. Br (a) CH3 – CH – CH2 – CH3 (b) | Br C|H3 — C|H3 CH3 — C — CH2 Br CH3 — C — CH — CH3 (c) | (d) | | CH3 CH3 Br https://t.me/studyzee

324 2. Match the column : Column (I) Column (II) No. of possible products. E2 reaction (including stereoisomerism) (elimination bimolecular) (p) 0 Br (q) 1 (a) ¾¾alc¾. KO¾¾H ® (r) 2 D (s) 3 (b) Br ¾ ¾alc¾. KO¾¾H ® D (c) Br ¾ ¾alc¾. KO¾¾H ® D (d) Br ¾¾alc¾. KO¾¾H ® D 3. Match the Column : HEM = Hoffmann exhaustive methylation followed by elimination. Column (I) Column (II) Reaction Product (a) ¾¾HE¾M ® ¾¾HE¾M ® (p) H2C == CH — CH2 — CH == CH2 N (q) H2C == CH — CH2 — CH2 — CH == CH2 H ¾¾HE¾M® ¾¾HE¾M® (b) N H ¾ ¾HE¾M ® ¾ ¾HE¾M ® CH3 (c) N (r) | H H 2C == CH — CH 2 — C == CH 2 (s) C|H3 ¾ ¾HE¾M ® ¾ ¾HE¾M ® (d) N H2C == CH — CH — CH == CH2 H https://t.me/studyzee

4. Match the column : 325 Column (II) Column (I) (p) Product are Diastereomers (q) Carbocation is intermediate (a) OH ¾H¾Dr® (r) 2nd order reaction (s) Ist order reaction (b) alc. KOH Column (II) Br ¾¾¾D ¾® (p) Optically active product (q) Optically inactive product (c) OH ¾H¾Dr® (r) 2nd order reaction alc. KOH (s) unimolecular reaction (d) Br ¾¾¾D ¾® 5. Match the column : Column (I) Cl alc. KOH (a) ¾¾¾® Cl Cl Cl alc. KOH (b) ¾¾¾® Cl Cl Cl H (c) ¾aq¾. K¾OH® Cl (d) ¾aq¾. K¾OH® CH3 https://t.me/studyzee

326 6. Match the column : Column (I) Column (II) Number of products E2 reactions (including stereoisomerism) (elimination bimolecular) (p) 1 (q) 2 (a) CH3 - CH2 - CH2 - CH2 - Br¾¾alc¾. KO¾¾H ® (r) 3 (b) CH 3 - CH - CH2 - CH3 ¾ ¾alc¾. KO¾¾H ® | Br CH 3 | (c) CH 3 -C - CH 2 - CH3 ¾ ¾alc¾. KO¾¾H ® | Br Ph - CH2 - CH - CH 2 - CH3 | (d) (s) 4 Br 7. Match the column : Column (I) Column (II) (p) E1 (a) ¾H¾+® ( A) OH D ¾ ¾Na¾NH¾2 ® (q) E2 (b) D Cl O || (c) CH3 – C – CH2 – CH – CH3¾ ¾EtO¾N¾a ® (r) Ei (elimination intramolecular) | D Br (d) Å Me ¾¾® (s) E1CB D N | Me OQ https://t.me/studyzee

8. Match the column : 327 Column (II) Column (I) Product Reaction D Å Me (p) H N Me (q) CH3 (a) OQ ¾¾® (r) HD (s) CD3 D Å Me N Me (b) OQ ¾¾® DD H Å Me N Me OQ ¾¾® (c) D H CH3 OQ Me N Me (d) Å ¾¾® DD CD3 9. (a) Br ¾¾alc.¾KO¾H ® (X) products (b) Br ¾¾alc.¾KO¾H ® (Y) (c) ¾¾alc.¾KO¾H ® (Z) Br CH3 H ¾¾alc.¾KO¾H ® (P) (d) CH3 Br CH3 Sum of X + Y + Z + P = https://t.me/studyzee

328 O || 10. Reaction-1 : Ph – C – CH3 ¾¾PC¾l5 ® ¾x¾N¾aN¾H2® ¾C¾H¾3I ® Ph – C º C – CH 3 Br Reaction-2 : ¾y¾N¾aN¾H2® CH 3 – C º C – CH 3 Br Reaction-3 : Ph – CH – C|H2 ¾z¾N¾aN¾H2® ¾¾Et¾-I ® Ph – C º C – Et | Cl Cl x, y, z are moles used. Sum of [ x + y + z = ] 11. Sum of a-hydrogen in major product of the reaction. OH Reaction-1 ¾¾H¾+ ® ( A) D OH Reaction-2 ¾¾H¾+ ® (B) Reaction-3 D OH ¾¾H¾+ ® (C) D OH Reaction-4 ¾¾H¾+ ® (D) D Sum of a-hydrogen is A + B + C + D = C|H3 C|H3 ¾¾H¾+ ® ( A) CH3 — C — CH — CH3 12. Reaction-1 | D OH Reaction-2 C|H3 ¾¾H¾+ ® (B) Reaction-3 CH3 – CH – CH2 – CH2 – OH D CH3 C|H3 CH – CH – CH2 – OH ¾¾H¾+ ® (C) CH3 D Sum of a-hydrogen is (A + B + C = ) https://t.me/studyzee

329 13. Reaction-1 OH ¾¾H¾+ ® ( A) D (major) Reaction-2 ¾¾H¾+ ® (B) OH D (major) Reaction-3 OH ¾¾H¾+ ® (C) D (major) Sum of a-hydrogen (A + B + C) = 14. (a) ¾¾H¾+ ® ( x) (b) ¾¾H¾+ ® ( y) OH D OH D OH (d) ¾¾H¾+ ® ( p) (c) ¾¾H¾+ ® (z) D OH D Total number of products obtained in above reactions including minor products is (including stereoisomer) 15. Match the column (I) and (II). Column (I) Column (II) Type of Reaction Reaction SN1 (a) R -2 -chlorobutane ¾¾KS¾H ® (p) SN2 acetone (q) E1 (r) E2 (b) R - 2- chlorobutane ¾¾EtO¾- N¾Å¾a ® (s) EtOH (c) 2 - bromo- 2- methyl propane ¾¾H2¾O ® (d) 2- butanol ¾ ¾H2S¾O¾4 ® D https://t.me/studyzee

330 Column (II) 16. Match the column (I) and (II). Type of Reaction (p) SN1 Column (I) Reaction (q) SN2 Cl (r) E1 (a) ¾ ¾aq.¾KO¾¾H ® (s) E2 Cl (b) ¾ ¾alc¾. KO¾¾H ® Cl (c) ¾ ¾H2¾O ® OH (d) ¾¾H¾+ ® D 17. Select whether the following reagent combination will result in elimination or substitution reactions leading to the major product. Reaction Substitution Elimination CH 3 | (a) CH 3 — C — Cl – | ¾¾KžOC¾(CH¾3 ¾)3 ® H2O H CH 3 | ¾¾H2S¾O¾4 ® (b) CH 3 — C — OH | D CH 3 https://t.me/studyzee

Cl 331 | (c) CH 3 — CH— CH 2 — CH 3 ¾¾alc-¾KO¾H ® Column (II) Comment on product CH 3 | Å– Racemic mixture (d) CH 3 — C — I ¾¾Na¾N¾3 ® Major product consist of even | H number of a-hydrogen Will not undergo dehydration Cl (e) CH3¾¾EtO¾- ® D CH 3 | (f) CH 3 — C — Cl ¾¾H2¾O ® | CH 3 18. Match the Column (I) and (II) (Matrix). Column (I) Reaction CH3 (a) ¾ ¾H¾+ ® (p) D OH CH3 (b) ¾ ¾H¾+ ® (q) D OH OH (c) ¾ ¾H¾+ ® (r) D https://t.me/studyzee

332 (d) ¾ ¾H¾+ ® (s) Major product consist of odd number of a-hydrogen OH D 19. For each of the following amines (A through D), exhaustive methylation (treatment with excess methyl iodide), followed by Hoffmann elimination (heating with AgOH), repeated as necessary, removes the nitrogen atom in the form of trimethylamine. Indicate the number of repetitive Hoffmann eliminations required to remove the nitrogen by a number (1 to 4) in the designated answer sheet. A. N B. N–H C. N D. NH2 E. N – H F. N a. b. c. d. e. f. 20. N ¾¾® x is total number of HEM (Hoffman Exhaustive Methylation and eliminations) to remove nitrogen from given compound. ¾¾alc.¾KO¾H ® y is total number of possible E 2 product (including stereoisomer) Br Sum of x+y= ? 21. CH3 CH3—CH—CH—CH3 (SN1 + E1) products. ( including stereoisomer) Br ¾¾EtO¾H ® (x) consider all products Total number of products are : https://t.me/studyzee

333 ANSWERS — LEVEL 2 1. A – a; B – a; C – b; D – c; E – c; 2. a – s; b – r; c – q; d – p 3. a – s; b – r; c – q; d – p 4. a – p, q, s; b – p, r; c – q, s; d – r 5. a – p, r; b – p, r; c – p, r; d – q, r 6. a – p; b – r; c – q; d – s 7. a – p; b – q; c – q; d – r 8. a – p; b – q; c – r; d – s 9. X = 3, Y = 3, Z = 2, P = 0 Þ 3 + 3 + 2 + 0 = 8 10. x = 3, y = 2, z = 3 Þ 3 + 2 + 3 = 8 11. 32 12. 33 13. 28 14. x = 3, y = 1, z = 3, p = 2 Sum = 9 15. (a – q), (b – s), (c – p), (d – r) 16. (a – q), (b – s), (c – p), (d – r) 17. Substitution – d, f Elimination – a, b, c, e 18. a – p, q; b – p, q; c – q; d – r 19. a – 3; b – 2; c – 3; d – 1; e – 2; f – 3 20. 6 21. 6 https://t.me/studyzee

334 5C ALKYL HALIDES Level - 1 Br 1. One eq. NaCN 1. ¾¾¾¾¾¾® (A); Product (A) is : 2. LiAlH4 Br Br Br (a) (b) CH2–NH2 CH2NH2 CH2NH2 CH2–NH2 (c) (d) Br Br https://t.me/studyzee

335 2. In the reactions given below, R – Cl ¾(¾i) K¾CN¾, (i¾i) L¾iAl¾H4® Product A R – Cl ¾(i¾) A¾gCN¾, (¾ii)¾LiA¾lH®4 Product B the compounds A and B are : (a) chain isomers (b) position isomers (c) functional isomers (d) metamers 3. Which is the major product expected from the following SN2 reaction ? Cl O ¾N¾aO¾¾H ® Product OH O (b) OH O (a) Cl OH OH OH (c) (d) 4. Consider the following E1 SN1 reaction : Br CH3 OH CH3 CH3 H3C H ¾E¾thHa¾n2Oo¾l¾D ® H3C H + H3C H The missing product(s) is(are) : OH CH3 CH3 CH3 (1) (2) H3C H H CH3 (3) H (4) H3C H (a) 1, 2 and 3 (b) 3 and 4 (c) 2 and 3 (d) 1,2,3 and 4 https://t.me/studyzee

336 5. What is the product of the following SN2 reaction ? OTs O ¾¾Na¾Br ® Product Ph OMe SN2 O OMe O OMe O OMe O OMe (a) H3C H (b) H3C H (c) H CH3 (d) H CH3 Br HH Br Br HH Br Ph Ph Ph Ph 6. Select the reagent that will yield the greater amount of substitution on reaction with CH 3 - CH 2 - Br : (a) CH 3CH 2OK in dimethyl sulfoxide (DMSO) (b) (CH 3 )3 COK in dimethyl sulfoxide (DMSO) (c) Both (a) and (b) will give comparable amounts of substitution (d) Neither (a) nor (b) will give any amount of substitution 7. Under the specified conditions, substrate X undergoes substitution and elimination reactions to give products A - D. A and B are stereoisomers, but not enantiomers. C and D are enantiomers. A is not an isomer of C. Which of the following could be the starting material X ? X ¾H¾2¾O ® A + B + C + D D Br Br CH3 Br CH3 H (III) (IV) Br CH3 (I) (II) H3C H H3C H H3C H H CH3 (a) (I) (b) (II) (c) (III) (d) (IV) CH 3 ¾ CH ¾ Br CH 3 CH 3 ¾ CH ¾ CH 3, | | (c) 8. CH 3 ¾ C ¾ CH 3 , Br | Br (b) (a) Compare rate of E 2 reaction : (a) c > b > a (b) a > b > c (c) b > a > c (d) c > a > b 9. Which reaction results in the formation of a pair of enantiomers ? (a) ¾ ¾CN¾–¾® (b) I H ¾H¾2¾O ® I DMSO (d) ¾C¾H3¾O¾H ® H3C I H (c) H I ¾D¾OMH¾F– ® https://t.me/studyzee

337 10. Rate limiting SN1 follows the sequence d+ d – R+ Br – R+ Br – R+ Br – R–Br (c) (a) (b) True statement about sequence on the basis of assumption that R contains 3 different groups is : (a) more stable carbocation, greater is in the proportion of racemization (b) the more nucleophilic the solvent greater in the proportion of inversion (c) In above sequence (b) represent separately solvated, pair of ions (d) All of these 11. Compare the two methods shown for the preparation of carboxylic acids : Method 1 : RBr Mg ¾1¾. C¾O¾2 ® RCO 2H Method 2 : ¾d¾iet¾hyl¾eth¾¾er ® RMgBr 2. H3O+ RBr ¾N¾aC¾¾N ® RCN ¾H¾2O¾, H¾¾Cl ® RCO 2H heat Which one of the following statements correctly describes this conversion ? Br CO2H (a) Both method 1 and method 2 are appropriate for carrying out this conversion (b) Neither method 1 nor method 2 is appropriate for carrying out this conversion (c) Method 1 will work well, but method 2 is not appropriate (d) Method 2 will work well, but method 1 is not appropriate 12. Which of the following statements is true ? (a) CH 3CH 2S- is both a stronger base and more nucleophilic than CH 3CH 2O - (b) CH 3CH 2S- is a stronger base but is less nucleophilic than CH 3CH 2O - (c) CH 3CH 2S- is a weaker base but is more nucleophilic than CH 3CH 2O - (d) CH 3CH 2S- is both a weaker base and less nucleophilic than CH 3CH 2O - 13. In the given pair of alcohols, in which pair second alcohol is more reactive than first towards hydrogen bromide ? CH3 OH H OH (a) and OH CH – CH3 (b) and | OH https://t.me/studyzee

338 (c) CH 3 - CH - CH 2 - CH 3 and CH 3 - CH 2 - CH - CH 2 - OH | | OH CH 3 (d) CH 3 - CH - CH 2 - CH 3 and (CH 3 )2 C - CH 2 - CH 3 | | OH OH 14. Which product would be expected to predominate in the given reaction ? OSO2CF3 OCH3 ¾C¾H3¾O¾H ® (a) D(30°C) O – SO2 – CH3 (c) (b) (d) None of these 15. Which is the major product of the following reaction ? N C ¾N¾aO¾H(¾exc¾es¾s) ® Product H 2O CH2– Br heat O (b) N C C OH OH (d) CH2– OH N (a) C CH2– Br O C OH (c) CH2– OH CH2– OH Br H CH3 D 16. H H ¾A¾lc.¾KO¾¾H ®( A) ; Major product of this reaction is : OH D CH3 D CH3 CH3 D (d) (a) H (b) (c) https://t.me/studyzee

339 17. Rate of SN2 reaction is : Br Br Br (A) (B) (C) (a) (B) > ( A) > (C) (b) (C) > ( A) > (B) (c) ( A) > (B) > (C) (d) ( A) > (C) > (B) 18. 1-2-dichloro ethane + NaSCH 2CH 2SNa ¾® C 4H 8S2 + (P) Unknown product (P) of the above reaction is : S S (a) (b) S S (c) H - S - C = C - CH = CH - S - H (d) H - C = C - CH = CH - S - H || || HH HH Br 19. ¾M¾ois¾t A¾g 2O® ( A) product Major product (A) is : OH OH OH OH (c) (d) (a) (b) 20. MeO Cl ¾K¾C¾N ® Product of reaction is : (MOM chloride) (Methoxy methyl chloride) Cl CN MeO CN (a) (b) (c) Me - O - CH 2 - CH 2 - CN (d) O CN CN 21. In the given pair of compound, in which pair the second compound is more reactive than first toward SN2 reaction ? (a) Cl or (b) CH2 – Cl or Cl Cl Br Br (c) or (d) or Cl Cl https://t.me/studyzee

340 22. Which compound might be synthesized by the SN2 displacement of an alkyl-halide ? SCH2CH3 (a) CH2 – OH (b) (c) Me 3C - OCH 3 (d) All of these 23. Identify C in the following series C 3H7I ¾K¾aOlc¾H. ® A ¾N¾B¾S ® B ¾K¾aClc¾N. ® C. D (a) (CH 3 )2 CH - CN (b) CH 2 = CH - CH 2CN (c) Br - CH = CH - CN (d) CH 2 = CH - CH CN | Br 24. What sequence of reagents is required to accomplish the following transformation ? OH (a) (1)NBS, ROOR (2) CH 3CH 2O - (3) 2HBr (4) NH - (5) disiamyl borane (6) H 2O 2 ,OH - 2 (b) (1) Cl 2 hn (2) OH - , heat; (3) 2HCl (4) OH - , heat (5) HgSO 4 , H 2SO 4 (c) (1) NBS, ROOR; OH -, DMSO (d) (1) Br2 , hn (2) t-butoxide (3) BH 3, THF (4) H 2O 2 , OH - 25. Which of the reagents shown below would accomplish the following transformations? Br 1. A OH 2. B AB (a) H 3O + BH 3 - THF; H 2O 2/NaOH (b) NaOH BH 3 - THF; H 2O 2/NaOH (c) HBr in ether Hg(OAc)2/H 2O; NaBH 4 (d) NaNH 2 Hg(OAc)2/H 2O; NaBH 4 26. What are the products obtained from the following reaction ? Br ¾H¾C¾ºº C¾N¾a ® Product Et 2O H H C C C C (a) + (b) + 20% 80% 20% 80% H (d) 100% C C C (c) C H 100% https://t.me/studyzee

341 27. The back-side attack on 2-bromobutane by methoxide (CH 3O - ) gives the product shown below. Which Fischer projection represents 2-bromobutane used as the reactant in this reaction ? OCH3 product = Et Me H Et Et Me Br (a) Me H (b) H Br (c) Br H (d) Me H Br Me Et Et 28. Consider the following statements : (1) Bridgehead halides are inert towards both S N1 and SN2 reactions (till one of the ring size is eight member ring) (2) The first step in both SN1 and E 1 reactions is the same (3) SN2 reactions proceed with total retention of configuration (4) E 2 eliminations are by the use of a solvent of low polarity and high concentration of a strong base Which of the above statements are correct? (a) 1, 2 and 4 (b) 1 and 3 (c) 2, 3 and 4 (d) 1, 2, 3 and 4 29. Consider the following alcohols : CH2OH CH2OH CH2OH CH2OH (I) O2N (II) CH3O (III) Br (IV) The order of decreasing reactivities of these alcohols towards substitution with HBr is : (a) III > I > IV > II (b) III > I > II > IV (c) I > III > IV > II (d) I > III > II > IV 30. In solvolysis of 1,2-dimethyl propyl p-toluene sulfonate in acetic acid at 75°C, how many (alkene + substitution) products will be formed ? (a) 2 (b) 3 (c) 4 (d) 5 31. Benzotrichloride reacts with milk of lime to form : (a) Benzal (b) Benzoic acid (c) Benzyl alcohol (d) Phenol 32. Br - CH 2 - (CH 2 )2 - CH 2 - Br + CH 3NH 2 ¾® Product of the reaction is : (a) (b) (c) (d) N N N N HH 33. The configurations of the reactant and the product in the following reaction, respectively, are: https://t.me/studyzee

342 CO2CH3 KCN CO2CH3 D Br EtOH CHCN HD (a) R, R (b) R, S (c) S, R (d) S, S 34. 1-4-dichlorohexane (1 mole) + NaI (1 mole) ¾A¾ce¾ton¾e ® Product of the reaction is : (a) Cl – CH 2 – CH 2 – CH– CH 2 – CH 3 (b) I – CH 2 – CH 2 – CH– CH 2 – CH 3 | | I Cl (c) H 2C = CH – CH– CH 2 – CH 3 (d) I – CH 2 – CH 2 – CH 2 – CH– CH 2 – CH 3 | | Cl Cl 35. Alkyl halides can be obtained by all methods except : (a) CH 3CH 2OH + HCl ZnCl 2 ¾® (b) CH 3 – CH 2 – CH 3 – CH 2 ¾C¾l2 ¾/UV¾lig¾¾ht ® (c) C 2H 5OH + NaCl ¾® (d) CH 3COOAg + Br2 CCl 4 ¾® 36. In order to prepare 1-chloropropane, which of the following reactants can be employed ? (a) Propene and HCl in the presence of peroxide (b) Propene and Cl 2 followed by treatment with aq. KOH (c) Propanol-1 and SOCl 2 pyridine (d) Any of the above can be used 37. Which alkyl halide has maximum density ? (a) C 3H7I (b) C 2H 5I (c) CH 3I (d) CH 3Br 38. Which of the following molecules would have a carbon-halogen bond most susceptible to nucleophilic substitution ? (a) 2-fluorobutane (b) 2-chlorobutane (c) 2-bromobutane (d) 2-iodobutane 39. When benzyl chloride is treated with ethanolic KCN, the major product formed is : (a) benzyl ethyl ether (b) benzyl alcohol (c) benzyl cyanide (d) benzyl isocyanide 40. Which of the following is most reactive towards nucleophilic substitution reaction ? 41. (a) CH 2 = CH – Cl (b) C 6H 5Cl (c) CH 3CH = CHCl (d)ClCH 2 – CH = CH 2 42. Which of the following reaction will not give ether as a major product ? (a) CH 3CH 2Cl + Ag 2O(dry) ¾® (b) (CH 3 )3 CCl + CH 3CH 2O -Na + ¾® CH 3 (c) CH 3CH 2Cl + Na + O - ¾® | (d) CH 3Cl + Na+O – – C – CH 3 ¾® | CH 3 O H+ (A) || OQ– S – OQ CH3 –I (B) Product (A) and (B) in above reaction is : https://t.me/studyzee

343 OO OO || || || || (a) O - — S — O — H ,O- — S — O — CH 3 (b) O - — S — O — H ,O -— S — CH 3 Å| O- OO OO || OQ—ÅS|| || || (c) O- — S— O - CH 3, | — H (d) O -— ÅS — O , O - — S — O - | || CH3 H CH3 43. Which of the following would be true for the reaction shown ? CH3OH Br OCH3 (a) The rate of the reaction depends only on the alkyl bromide concentration. (b) The rate of the reaction depends only on the methanol concentration. (c) The rate of the reaction depends on both the alkyl halide concentration and the methanol concentration. (d) The rate of the reaction depends on the concentration of neither reactant. 44. The correct order of rate of SN 1 is : Cl Cl (b) < Cl (a) > Cl H Cl Cl Cl (d) < (c) Cl > 1. (c) 2. (c) ANSWERS — LEVEL 1 6. (a) 7. (c) 8. (b) 9. (b) 10. (d) 14. (a) 15. (c) 16. (c) 17. (c) 18. (a) 3. (b ) 4. (a) 5. (a) 22. (d) 23. (b) 24. (d) 25. (d) 26. (b) 11. (c) 12. (c) 13. (d) 30. (d) 31. (b) 32. (b) 33. (d) 34. (d) 19. (c) 20. (b) 21. (d) 38. (d) 39. (c) 40. (d) 41. (b) 42. (b) 27. (d) 28. (a) 29. (a) 35. (c) 36. (c) 37. (a) 43. (a) 44. (b) https://t.me/studyzee

344 Level - 2 1. The following organic halide derivatives (A to J) are reacted in ethanol solution with each of the nucleophiles : acetate, methylthiolate, cyanide and hydroxide anions. Six possible results from these combinations of reactants are designated (1) through (6) below : Write the number corresponding to your best estimate of the outcome of each reaction in the appropriate answer box below. Cl CH2 – Cl H3C Cl A B H3C Cl Cl Br G CH 3 – I H CH3 F C DE H CH2 – Br H Br Br H H3C CH3 HH H H3C IJ H Possible Outcome : (2) Substitution (1) No reaction (4) Substitution and elimination (3) Elimination (6) No reaction or slow elimination (5) No reaction or slow substitution Compound AB CDE F GHI J (i) CH 3CO 2Na (ii) CH 3SNa (iii) NaCN (iv) NaOH https://t.me/studyzee

345 2. In each of the following sections three organic halogen compounds are listed. In the box given enter a number (1 to 3) indicating the order of reactivity of the designated (1 is most reactive and 3 is least). (a) SN 2 substitution by NaOCOCH 3 in methanol: 1. (CH 3)2CHBr CH 3CH 2CH 2Br £ 2. £ 3. CH 2 = CHCH 2Br £ (b) SN2 substitution by NaI in acetone: 1. C 6H 5Cl 2. C 6H 5CH 2Cl £ £ 3. C 6H 5CHClCH 3 £ (c) SN2 substitution by NaCN in methanol: 1. CH 3CH 2Cl 2. CH 3CH £ 2F £ 3. CH 3CH 2I £ (d) SN 2 substitution by NaSCH 3 in methanol: 1. 2. (CH 3)2CHCH 2CH 2Br£ CH 3CH 2CHBrCH 2CH 3£ 3. (CH 3)3CCH 2Br £ 3. Isobutyl alcohol (2-methyl-1-propanol), (CH 3)2CHCH 2OH, can be transformed to each of the compounds (a through l) listed in the left-hand column. In each case the number of steps needed to accomplish the change is noted, and an answer box is provided for your reagent selections. Fourteen reagents (designated A through N) are listed in the right-hand column. Write letters designating the reagent or reagents you believe will achieve the desired transformation in the box to the right of the product formula. In the case of a multi-step sequence write the reagents in the order they are to be used. In some cases you may wish to use a previously prepared compound as a reactant. If so, write the number (a to l) corresponding to the desired compound. Desired product No. of Write Reagent List Steps Options a. (CH 3)2CHCH 2Br b. (CH 3)2C = CH 2 one A. Hg(OAc)2 in H 2O c. (CH 3)2CHCH = O one B. PBr3 & heat d. (CH 3)2CHCO 2H one C. NaBH 4 in alcohol e. (CH 3)3CBr one D. LiAlH 4 in THF (aqueous workup) f. (CH 3)2CHCH 2C º N two E. NaCN in alcohol g. (CH 3)2CHCH 2OCOCH 3 two F. PCC in CH 2Cl 2 h. (CH 3) 2CHCO 2C 2H 5 one G. Jones' reagent (CrO 3 in H 3O + ) i. (CH 3)2CHCH 2OCH 2(CH 3) two H. HBr in CH 2Cl 2 j. (CH 3)3COH two I. H 3PO 4 and heat k. (CH 3) 2CHCH 2NH 2 three J. (CH 3CO)2O + pyridine l. (CH 3) 2CHCH 2CH 2NH 2 three K. NaN 3 in aqueous alcohol two L. C 6H 5CO 3H in CH 2Cl 2 (peracid) M. NaH in ether and heat N. C 2H 5OH + acid catalyst & heat https://t.me/studyzee

346 Subjective Problems CH3 1. CH3OH ? Br X = Total number of substitution and elimination product(s). Find the value of X. ANSWERS — LEVEL 2 1. AB C DE F GHI J (i) 2 2 2 1 1 1 6 2 2 6 (ii) 2 2 2 1 1 5 6 2 2 6 (iii) 2 2 2 1 1 1 3 3 2 3 (iv) 4 2 2 1 1 5 3 3 4 3 2. a – 3 > 1 > 2; b – 2 > 3 > 1; c – 3 > 1 > 2; d – 1 > 2 > 3 3. a – B; b – I; c – F; d – G; e – I, H or 2 H; f – B, E or 1, E; g – J; h – G, N or 4N i – N, j – I, A, C or 2AC or ILD or 2LD; k – B, K, D or 1KD; l – B, E, D or 1ED or 6D Subjective Problems 1. 4 https://t.me/studyzee

347 6 ALCOHOL, ETHERS AND EPOXIDES Level - 1 1. The following transformation involves a carbocation rearrangement. The carbocation is generated by protonation of the hydroxyl group, followed by the loss of water. Which bond has to migrate in the carbocation to yield the product indicated (after the deprotonation) ? OH H2SO4 (b) H (c) (d) (a) (c) c (a) a (b) b (d) d 2. Identify the major product. HO ¾H¾2S¾O¾4 ® Product (a) (b) (c) (d) https://t.me/studyzee

348 CH2 – OH O || Et CH2 – C– Cl (A) (major) 3. N | H O CH2 – OH || (b) Et CH2 – O – C – CH3 Et (a) N N | | H C – CH3 || O O || CH2 C – CH3 Et (c) N (d) N | | HH 4. Predict the product when given compound reacts with LiAlH 4 : OO || || C C OCH3 H || (A) O OH O OH O || (b) || (a) C – O – CH3 C – O – CH3 || O OH OH OH OH O || (c) C H (d) OH OH https://t.me/studyzee

349 5. Predict the product when given compound (A, in the above question 4) reacts with NaBH 4 . OO || || OH C – O – CH3 OH C – O – CH 3 (a) OH (b) OH || O OH O OH || C (c) H (d) OH OH O O C–O–H HCl C – O – CH3 + H2O 6. + CH3 – O 18 – H Catalyst The labelled –O18 will be in : Methyl benzoate (a) H 2O (b) Methyl benzoate (c) Both (a) and (b) (d) Benzoic acid 18 7. CO 2H CH 2 – OH ¾H¾+ ® (A); Product (A) is : | + | 18 CO 2H CH 2 – OH D O O || 18 || C – O – CH 2 C – O – CH 2 (a) | | (b) | | C – O – CH 2 C – O – CH 2 || || 18 O O 18O || OO C – O – CH 2 || || (c) | | (d) H – O – C – C – O – CH 2 – CH 2 – OH C – O – CH 2 || 18O 8. Which is oxidized most easily ? (a) CH 3 – CHOH – CH 3 (b) OH (c) CH 3 – CH 2 – O – CH 2 – CH 3 CH3 (d) OH https://t.me/studyzee